DECLARATION

I hereby declare that, the project entitled “Preparation and Characterization of

ZnS Thin Films Using Chemical Bath Deposition (CBD) Method” submitted for
the degree of award of Master of Science in the faculty of Science of the Pune
university is completed and written by me, has not previously formed the basis
for the award of any Degree of University or examining body to the best of my
knowledge.

Place: Parner Project Student

Date: (Miss. Zaware V.A)
 INDEX

Content Page no.

CHAPTER 1: Introduction ............................................................... 8-13

1.1 Thin film Introduction ………………………………………………… ......

1.2(A) Physical properties of thin films ……………….......................................

1.2(B) Classifications of Thin Film Deposition Techniques …………….....

1.3 THIN FILM DEPOSITION METHODS...............................................

1.4 Applications of Thin Films.................................................................

1.5 Literature survey................................................................................

CHAPTER 2: THEORETICAL BACKGROUND OF CBD................... 14-20

2.1 INTRODUCTION...............................................................................

2.2 THEORETICAL BACKGROUND OF CBD.....................................

2.3 SELECTION OF DEPOSITION PROCESS.......................................

2.4 SYNTHESIS OF ZnS THIN FILM BY CBD METHOD....................

2.5 ADVANTAGES OF THE CBD METHOD.........................................

2.6 THIN FILM THICKNESS CONTROL...............................................

2.7 EXPERIMENTAL..............................................................................

2.8 CONCEPT OF SOLUBILITY AND IONIC PRODUCTS.................

2.9 CBD METHOD FOR DEPOSITION OF METAL OXIDES AND

CHALCOGENIDES...............................................................................

CHAPTER 3: CHARACTERIZATION TECHNIQUES ................. 20-28

3.1 INTRODUCTION.............................................................................

3.2 X-RAY DIFFRACTION (XRD).......................................................

3.3 UV-VIS SPECTROSCOPY...............................................................

3.4 SCANNING ELECRON MICROSCOPY (SEM)...........................

CHAPTER4: EXPERIMENTAL WORK AND INSTRUMENTATION .. 28-34

4.1 CHEMICALS......................................................................................

4.2 ELECTRONIC BALANCE................................................................

4.3 PH INDICATOR.................................................................................

4.4 MAGNETIC STIRRES AND HEATER...........................................

4.5 PREPARATION OF SOLUTION.....................................................

4.6 EXPERIMENTAL PROCEDURE...................................................

CHAPTER 5: RESULT AND DISCUSSION .................................. 35-38

5.1 XRD RESUIT OF ZnS THIN FILM................................................

5.2 PARTICAL SIZE FROM FULL WIDTH HALF MAXIMA........

5.3 SEM RESULT OF ZNS..................................................................

5.4 UV RESULT................................................................................

CHAPTER 6: CONCLUSION...............................39
REFRENCES ........................................................... 40
 ABSTRACT
Chemical bath deposition of ZnS thin films from NH3/SC (NH2)2/ZnSO4 solutions has been
studied. The effect of various process parameters on the growth and the film quality are
presented. The influence on the growth rate of solution composition and the structural, optical
properties of the ZnS thin films deposited by this method have been studied. The XRF analysis
confirmed that volume of oxygen of the as deposited film is very high. The XRD analysis of as-
deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed
films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results
confirmed that the as-deposited films have amorphous Zn (OH) 2. SEM studies of the ZnS thin
films grown on various growth phases show that ZnS film formed in the none-film phase is
Discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular
structure with the grain size about 100 nm. There are adsorbed particles on films formed in the
saturation phase.
Transmission measurement shows that an optical transmittance is about 90% when the
wavelength over 500 nm. The band gap (Eg) value of the deposited film is about 3.51 eV.
CHAPTER 1: INTRODUCTION
1.1 Thin film
Recently, thin films have been used in the study of the relationship between the
structure of solids and their physical properties. Practical application of thin film includes
electrical circuits, optical instruments and magnetic information-storage devices. Thickness of
the thin film is usually discussed in terms of angstrom units (Å).Thin films are formed by
depositing material onto a clean supporting substrate to build up film thickness, rather than by
thinning down bulk material. “Any solid or liquid object with one of its dimensions very much
less than that of the other two may be called a thin film”. A number of techniques have been
examined in the search for the most reliable and cheapest method of producing the thin film
These include oxidation of an evaporated metal film, reactive and nonreactive sputtering
techniques, chemical vapour deposition etc. Chemical spray Pyrolysis technique has been
developed in 1966 by Chamberlin and Sharman for the deposition of thin films Spray
Pyrolysis is a process in which a thin film deposited by spraying a solution on a heated
surface, where the constituents react to form a chemical compound. Spray Pyrolysis is a
versatile technique for thin film deposition. Now days thin film use in different modes i.e.
resistors capacitor as well as microelectronic devices .thin film required for solvent. Spray
Pyrolysis is simple and low cost method this method does not required for high temperature.
Spray Pyrolysis technique has been used to prepare the thin films on a variety of substrate like
glass, ceramic or metallic.

1.2 (A) Physical properties of thin films

The mechanical properties of thin films are quite different from those of the bulk
material. For e.g. the strengths exhibited by some films appear to be as much as 200 times as
great, as for well annealed bulk samples, and are usually several times as great as the strengths
of severely cold worked bulk material.
An electronic effect of thickness is observed in very thin dielectric films as an abrupt
change in the conductance at constant field as the thickness is reduced below some finite
dimension. With dielectric films thicker than about 100 Å, the field required to cause a given
current to flow is generally independent of film thickness. Thinner films, however exhibit a
large increase in current density due to “tunnelling”. This is because the probability of an
electron with a given energy penetration the potential barrier presented by the dielectric
increases exponentially with decreasing thickness.
 Thickness results also in a marked change in the conductivity of metallic films as film
thickness becomes of the same order as, or smaller than the electron mean free path. When
this occurs scattering of electrons at the film surface becomes a significant factor and the
effective conductivity is reduced. Observations of film resistivity as a function of thickness
thus provide one means of estimating the electron mean free path. This method has been found
different in practice, since films of a high degree of perfection are required. The resistivity of
metal films may be separated into thermal motion and another caused by scattering at lattice
imperfections. The imperfections in deposited metal films result in resistivity higher than
those observed for bulk metals. The effect of temperature on the two modes of scattering is
not the same and this result in differences between the temperature coefficients of resistance
of bulk metals and those of polycrystalline metallic films. The magnitude of this difference
may be used to infer the degree of imperfection in films.
The emerging technology needs various types of thin films for variety of applications.
Many materials have been prepared in the form of thin films over a century because of their
potential technical value and scientific curiosity in their properties. Thin film is defined as,
any solid or liquid system possesses at most 2-D order or periodicity. Properties of thin film
differ significantly from those of bulk to surface and interface effects; this dominates overall
behaviour of the thin films. Thin films have very wide range of applications and extend from
the micrometer dots in microelectronic, photo electronic, thermo electronic,
superconductivity, information- storage media, fuel cells, and bio-compatible coatings. Thin
film semiconductor science is the expanding field and studies on thin film semiconductor are
becoming interesting.
The properties of thin films depend on the method of deposition. The required
properties and versatility can be obtained by choosing proper method of thin films deposition.
Thin film deposition methods can be broadly classified as physical and chemical. Under
physical methods, we have vacuum evaporation, and sputtering, where the deposition takes
place after the material to be deposited has been transferred to a gaseous state either by
evaporation or an impact process. Under chemical methods, we have the gas phase chemical
processes such as conventional chemical vapour deposition (CVD), laser CVD, photo CVD,
metal organic-chemical vapour deposition (MOCVD), and plasma enhanced CVD, Liquid
phase chemical methods include electrodeposition, chemical bath deposition (CBD), modified
chemical bath deposition (M-CBD), successive ionic layer adsorption and reaction (SILAR),
electro less deposition, iodization, spray pyrolysis, liquid phase epitaxial, etc.
 The broad classification of thin film deposition technique is outlined in fig 1. Among
all these thin film deposition techniques, chemical bath deposition (CBD) method is well
suited for producing large area thin films. This method is low temperature method and it does
not require any sophisticated instruments. It involves deposition of semiconductor thin films
on substrates that are kept in the aqueous solutions.

1.2 (B) Classifications of Thin Film Deposition Techniques

Figure 1: Broad Classification of Thin Film Deposition Techniques

The thin film deposition techniques can be broadly classified as physical and chemical
methods. Physical methods involve vacuum evaporation and sputtering; the material to be
deposited has been transferred to a gaseous state either by evaporation or an impact process and
then deposited on the substrate. Under various chemical methods, therefore the gas phase
chemical processes such as conventional Chemical Vapour Deposition (CVD), Laser CVD,
Photo CVD, and Plasma Enhanced CVD. The liquid phase chemical techniques include Spray
Pyrolysis, Chemical Bath Deposition (CBD), Electrodeposition, Successive Ionic Layer
Adsorption and Reaction (SILAR) and Liquid Phase Epitaxial etc.
The broad classification of thin film deposition techniques is outlined in Fig. 5. The
physical methods are plugged with certain drawbacks and problems. A suspicious and precise
control of the boat temperature is a crucial requirement for finding good stoichiometric films
and to obtain the particular composition in alloy films. Chemical methods are comparatively
economical and easier ones as compared to physical methods. On the other hand, there is no
 ideal method to prepare the compounds and alloys in thin film form, which will satisfy all the
necessities. Spray Pyrolysis is a simple and low-cost technique for the preparation of
semiconductor films. Details information about various aspects of spray Pyrolysis is given in
review articles by many authors [1, 2]. The process is particularly useful for the deposition of
oxides such as ZnO, TiO2, WO3, etc. [3-5].
The SPT involves spraying of a solution containing soluble salts of the desired
compound onto preheated substrates, where the constituents react to form a chemical compound.
The chemical reactants used for making solution are selected such that the products other than
the desired compound are volatile at the temperature of deposition. Physical method covers the
deposition techniques which depend on the evaporation or ejection of the material from a
source, i.e. evaporation or sputtering, whereas chemical methods depend on physical properties.
Structure-property relationships are the key features of such devices and basis of thin film
technologies.
Underlying the performance and economics of thin film components are the
manufacturing techniques on a specific chemical reaction. Thus chemical reactions may depend
on thermal effects, as in vapour phase deposition and thermal growth. However, in all these
cases a definite chemical reaction is required to obtain the final .physical method required large
space.

1.3 THIN FILM DEPOSITION METHODS

1. SILAR Method

In SILAR method, to prepare thin film substrates are immersed into separately placed
cationic and anionic precursors and precipitate formation in the solution, i.e. wastage of the
material was thus avoided. Also, SILAR can be used to deposited compound materials on a
variety of substrates such as insulators, semiconductors, metal.

2. CBD Method

The chemical bath deposition (CBD) method is one of the cheapest methods to
deposited thin films and nanomaterials, as it does not depend on expensive equipment and is a
scalable technique that can be employed for large area batch progressing or continuous
deposition. In 1933 Brickman deposited lead sulphide (PbS) thin film by chemical bath
deposition (CBD) or solution grown method.
 3. Chemical Vapour Deposition (CVD)

Vapour phase precursors are brought into a hot wall reactor under conditions that favour
nucleation of particles in the vapour phase rather than the deposition of a film on the wall. It is
called chemical vapour deposition. Here organic metal gas is used. Deposition can also take
place due to chemical reaction between some reactance on the substrates.

4. Physical Vapour Deposition

Physical vapour deposition is a collective set of processes used to deposit nanomaterials.

PVD processes are environmentally friendly vacuum deposition technique. In PVD materials
can be deposited with improved properties compared to substrate material. In this method the
rate of coating deposition is usually small.

5. SOL-GEL Method

Sol-gel is chemical solution process used to make ceramics and glass materials in the
form of thin films, fibers or powders. A sol is a colloidal or molecular suspension of solid
particles of ions in solvent. The particle may be amorphous or crystalline. A gel is a semi rigid
mass that forms when the solvent from the sol begins to evaporate. It can produce thick coating
to provide corrosion protection performance.

6. SPRAY Pyrolysis

Spray pyrolysis is a well established and widely used technique for the film processing. It is
a chemical vapour deposition that has been successfully used for the deposition of various
oxides based materials. Two major interests in this method are operating at atmospheric pressure
and deposition on large surface. It is quite simple method due to use of air without vacuum
system which is mostly used in other technique. The spray deposition is based on the
mechanical transformation of the solution to droplets steam by using compressed gas or
ultrasonic waves. Basically pyrolysis is chemical reaction. This reaction involves molecular
breakdown of large molecules into smaller molecules in the presence of heat. Pyrolysis is also
known as thermal cracking, thermolysis, depolymerisation etc. At any given temperature
molecule is in vibrating stage this is called as molecular vibration. The frequency at which
molecules are vibrates is directly proportional to the temperature of the molecules. During
pyrolysis the object molecules are subjected to very high temperature leading to very high
molecular vibration then every molecule in the object stretched and shaken to extent that
molecules start breaking down into smaller molecules. This is pyrolysis technique.
1.4 Applications of Thin Films:

Although the study of phenomena dates back well over a century, it is really only over
the last four decades that they have been used to a significant extent in practical situations. The
requirement of micro miniaturization made the use of thin and thick films virtually imperative.
The development of computer technology led to a requirement for very high density storage
techniques and it is this which has stimulated most of the research on the magnetic properties of
thin films. Many thin film devices have been developed which have found themselves looking
for an application or, perhaps more importantly market. In general these devices have resulted
from research into the physical properties of thin film.

1.5 Literature survey

Now a days due to the over use of fossil fuels, environmental pollution, global warming
and rapid resource depletion, the technology advances in modern society have driven the
development of electrochemical power sources which offers “clean energy” exponential growth
in various portable electronic devices as well as interest in electric vehicle for clean air has
created intense worldwide activity in electrochemical power sources. There are several power
types of electrochemical power system. These are batteries, fuel cells and super capacitors (1-2).
The electrochemical power system of a several advantages compared to fuel combustion. First
of all they provide clean energy and attractive from an environmental point of view. Secondly
they are potentially more efficient than fuel combustion systems. Thirdly the electrochemical
systems are appealing in terms of world energy recourses in a more economical way.
Easy accessible source now present is the electrical energy which is not available at all time.
Consequently, there is need of development of improved methods for storing electrical energy
when it is available and retrieving when it is needed. Stored electrical energy is required in
many household as well as industrial applications e.g. cell phone, pagers, solar cell, computers,
satellites , standby power supply systems, hybrid electric vehicles etc. electrical energy can be
stored in two fundamental ways batteries and capacitor. Capacitor is the direct way of storing
electrical energy. Capacitors are very useful component and widely used in a electronic and
electrical circuit. Different techniques to prepare the ZnS film have been reported in the
literature, such as thermal evaporation, molecular beam epitaxial, spray pyrolysis, sputtering.
Among the previously mentioned techniques, chemical bath deposition (CBD) emerges as a
promising, simple, and low
CHAPTER 2: THEORETICAL BACKGROUND OF CBD

2.1. Introduction
Variety of techniques has been used to deposit different kinds of thin films. The choice
of a particular method/technique depends on factors like; 1) material to be deposited, 2) nature
of the substrate on which the film is to be deposited, 3) thickness of the film required, 4)
structure of the film expected and 5) application of the thin film. The deposition method
strongly affects the structure and hence physical properties of the material; therefore the proper
choice of the method is of key importance.

2.2 Theoretical background of CBD method

Basic Mechanism of Chemical Bath Deposition

The chemical bath deposition method for the preparation of thin films has recently been
shown to be an attractive technique because of it’s simplicity, convenience, low cost and low
temperature, and it has been successfully used for depositing ternary metal chalcogenides thin
films. Understanding of the chemistry and physics of the various processes involved in a
deposition process has now made possible to obtain undoaped, multi component semiconductor
thin films of usual/ unusual a metastable structure. The first two mechanisms involved free
sulphide ions. While the last two are based on breaking of the carbon–chalcogen bond and do
not involve formation of free chalcogenides chemical reaction either takes place on the surface
of the dipped substrate or in the solution itself, where the mixing of the components on the
surface to be coated is required. Most of the coatings are formed in a two step fashion;
i)”Sensitizing” the surface for the nucleation reaction of the adhering coating layer.
ii) Deposition of coating by selected reactions.
The most widely used deposition methods are listed below:
A) Homogeneous chemical reduction of a metal ion solution by reducing agent regardless the
substrates.
B) Electrolysis plating for the deposition of metallic coating by controlled chemical reduction
that is catalyzed by the metal or alloy being deposited.
C) Conversion coating forming a sacrificial layer containing compound of the metal substrate.
D) Displacement deposition or galvanic deposition makes use of the electro negativity
differences of the metal.
E) Arrested precipitation technique means a metal ion is arrested by organic complexing agent
which is then made available by slow dissociation of the organ metallic complex at specific
pH value. Among the various chemical deposition systems, chemical bath deposition has
attracted a great deal of attention because of its overriding advantages over the other
conventional thin film deposition methods.

2.3 Selection of Deposition Processes:

No single technique is ideally sustained for preparation of large area thin films with all
the desired properties. Hence choice and selection of deposition processes plays a vital role in
the formation of good quality thin films, and while selecting a particular technique, it should be
tested satisfactory for the following aspects:

Cost effectiveness

 It should be able to deposit desired material.

 Film microstructure and deposition rate should be controlled.
 Stoichiometry should be maintained as that of
 The starting materials.
 Operation at reduced temp.
 Adhesive at reduced temp.
 Abundance of deposit material.
 Scaling up of the process.
 Masking of the substrates.
 Control on film substrate interface and defects Created in the film.
Among the various techniques discussed above, arrested precipitation technique as well as
electro deposition technique used for synthesis of binary transition metal dichalcogenides and
hybrid process of these two is employed in the synthesis of ternary mixed transition metal
dichalcogenide in the present investigation.

2.4 Synthesis of ZnS thin film by CBD method

In spite of the fact that CBD has been in use for a long time and that the reactions
involved appear to be quite simple, the mechanisms of CBD process is often ambiguous. There
are several different mechanisms of CBD. These can be divided into four fundamentally
different types. Deposition of Nickel Sulfide is taken as an example. In these reaction process
for Deposition of Nis thin film, Contained Nickel Sulfide (0.5M) and Thiourea CS (NH 2)
2(0.25M). Then obtained NiS film were homogeneous with a WHITE colour and good adhesion
to the substrate

2.5 Advantages of the CBD method

The major advantage of CBD method is that it requires in its simplest form only solution
containers and substrate mounting device. Chemical Bath Deposition yields stable, adherent,
uniform and hard films with good reproducibility by a relatively simple proves. The growth of
thin films strongly depends on growth of conditions, such as duration of deposition, composition
and temp of the solution and topographical and chemical nature of the substrate. One of the
draw-back of this method is the wastage of solution after every deposition.

2.6 Thin films thickness control

The thin film thickness is controlled by optical techniques and the crystal monitor
techniques. The optical technique is usually applicable for interference coating and only for
visible region. In interference coating, optical film thickness is generally of quarter wave
thickness and in some cases of half thickness.

2.7 Experimental

The CBD method is presently attracting considerable attention as it does not require
sophisticated instrumentation like vacuum system and other expensive equipments. Simple
equipments like hot plate with magnetic stirrer are needed. The starting chemicals are
commonly available and cheap. The term ‘‘chemical bath deposition’’ is used here for method
that produces a solid film in a single immersion through control of the kinetics of formation of
the solid. If a change in the metals oxidation state occurs, it takes place in the bulk solution.
Many sulphides, selenides and oxides have been prepared by this method as summarized in
several review articles. The low temperature deposition avoids oxidation and corrosion of
metallic substrates. Chemical bath deposition results in pin hole free and uniform deposits since
the basic building blocks are ions instead of atoms. The preparative parameters are easily
controllable and better orientations with improved grain structure can be obtained. The details of
CBD method, mechanism of film formation etc. have been greatly described in the review by
Mane and Lokhande and also discussed in Gary Hode’s book entitled “Chemical Solution
Deposition of Semiconductor Films.
The processes that occur in the CBD solution consist of following steps:

1) Equilibrium between the complexing agent and water;

2) Hydrolysis of the chalcogenide/oxide source;
3) Formation/dissociation of ionic metal–ligand complexes; and
4) Formation of the solid
The CBD requires supersaturated solutions, i.e. the product of the concentrations of metal and
chalcogenides must exceed the solubility product of the desired solid. In a closed system,
growth cannot continue once the reactants have been depleted below this point. Thus, the
maximum obtainable thickness is limited by the supply of reactants. Increasing the degree of
super saturation (for example by raising the pH, in the case of oxides) increases the rate of film
growth, as reported by several groups. Three main factors, which affect the solubility product,
are temperature, solvent and particle size. The solubility of solution changes as a function of
temperature since increase in temperature increases stress, the equilibrium between a precipitate
and its ions in solution shifts according to whether the heat of solution is endothermic or
exothermic. The solubility constants are found to be dependent on temperature, medium and
method of measurements and therefore a difference of several orders of magnitude in solubility
constants of materials has been reported in literature.

Figure 2: The schematic diagram of CBD method.

2.8 Concept of solubility and ionic products

Sparingly soluble salt AB, when placed in water, a saturated solution containing A + and
B- ions in contact with undissolved solid AB are obtained and equilibrium is established
between the solid phase and ions in the solution as

AB (S) = A+ + B ------------------------------------ (2.1)

Applying law of mass action to this equilibrium,

K= C A+ C B- / C AB (S) -------------------------------- (2.2)

where, CA+, CB- and C AB are concentrations of A+, B- and AB in the solution, respectively.

The concentration of a pure solid phase is a constant number i. e.

CAB (S) = constant = K' ---------------------------- (2.3)

K = CA+CB - / K'

Or K K' = C +.C -
----------- (2.4)
A B

Since, K and K' are constants, the product K K' is also constant, say Ks. Therefore equation
(2.4) becomes,

KS = CA+.CB- ----------- (2.5)

Ks is called solubility product (SP) and (CA+CB-) is called as the ionic product (IP). When the
solution is saturated, the ionic product is equal to the solubility product. But when IP exceeds
the SP i.e. IP/SP = S > 1, the solution is supersaturated, precipitation occurs and ions combine
on the substrate surface and in the solution to form nuclei.

2.9 CBD method for deposition of metal oxides and chalcogenides

The CBD method for deposition of metal oxides and chalcogenides has been attracted a
considerable interest due to the simplicity of the method and relatively low temperature process.
The chemical deposition of metal oxides and chalcogenides is based on heating of alkaline
solution of metal salt. For example, when ammonium hydroxide is used to make the bath
alkaline, a heated solution of ammonia gradually loses ammonia. As ammonia is lost, the free
cations concentration will gradually increase. Number of free cations will also increase with an
increase in temperature, due to the decrease in the stability of complexes. Thus in CBD method;
the oxide films are often formed by reaction of hydroxide ions with a salt. However, in many
cases, metal hydroxide is formed along with oxide due to the aqueous alkaline nature of the
bath.

3 Effect of preparative parameters

The rate of deposition and terminal thickness depends upon the number of nucleation
centres, super saturation of the solution and rate of stirring. The growth kinetics depends on the
concentration of ions, their velocities, nucleation and growth processes on immersed substrates
the effect of various deposition conditions on these parameters are discussed below:

a) pH of the bath

For the growth of good quality thin films, the hydroxyl ions in precursor solution are
necessary. The thin film formation depends on the pH of the reaction mixture and pH depends
on OH ions. The reactivity of hydroxide ions with metal ions affects when pH of the solution
decreases. The decrease in pH results in porous, non-reflecting, powdery and weakly adhered
thin films on the substrates. Increasing the pH value above 9.5 results in to nonporous, uniform,
smooth, and tightly adherent and reflecting thin films. At higher pH metal ion concentration
will be lower and the reaction rate will be slow. So, throughout the experimental procedure of
deposition pH value is maintained at 10.5 ± 0.1.

b) Complexing agent

The deposition of thin film on glass surface is an adsorption phenomenon. Film

formation occurs by combination of released metal ions from complex metal ion source and
chalcogen source. The use of complexing agent to complexes metal ion, made free in alkaline
medium of pH value 10.5 ± 0.1. It helps to limit the hydrolysis of the metal ion and impart some
stability to bath otherwise it undergoes rapid hydrolysis and precipitation.

c) Temperature

It is observed that at room temperature, no film formation takes place. It may be due to
low temperature. Almost all the metal ions are in a complex bound state; there may not be free
ions for film formation. When temperature of the bath container is increased to 353 K good
quality and adherent films were deposited on glass substrates. The variation of film thickness
with temperature. It has seen that the terminal layer thickness is increased with increase in
temperature linearly up to 353 K and above 353 K it decreases. It is clear that at 353 K, thermal
energy is sufficient to make ions free from bound complex states which increase the rate of film
formation. Above 353 K temperature, the reaction gives precipitation rather than film which
settled down at the bottom of container as a result, layer thickness of thin film was found to be
decreased.

e) Substrate

Film formation takes place only under certain conditions i.e. either under optimum
conditions or when the substrate has special properties facilitating for the formation of single
crystal films. The second condition fevers the formation because when the lattice of the
deposited material matches well with that of the substrate, the free energy change is smaller,
thereby facilitating nucleation.
CHAPTER 3: CHARACTERIZATION TECHNIQUES

3.1 Introduction
There has been significant interest in the preparation of good quality thin films where
optimization of preparative parameters is of vital importance. The different characterization
techniques such as X-ray diffraction (XRD), UV-Vis spectroscopy and SEM etc. have been
employed for optimization of preparative parameters. So in this chapter we will discuss about
various techniques employed for thin film characterization.

3.2 X-RAY diffraction (XRD)

The X-ray diffraction (XRD) is well-known technique for characterization of bulk and
thin film samples. It is used to determine the crystal structure of materials. Fig.3 shows a
schematic diagram of X-ray diffractometer. Constructive interference occurs when the atomic
spacing is an integral multiple of the X-ray wavelength, producing in a characteristic diffraction
peak. By moving the detector and source across a range of different angles with respect to the
sample, a diffraction pattern can be obtained. This diffraction pattern is characteristic of a
material and the crystalline phases that are present in the sample. The structural identification
and determination of lattice parameters are based on the interpretation of X-ray diffraction
patterns.
The occurrence of X-ray diffraction involves of reflection of X-rays from the different
crystallographic planes of material and Bragg’s law governs it.
2d Sin θ = n λ
Where, d = lattice spacing for (hkl) plane,
 = wavelength of X-rays
n = order of diffraction (n =1)
 = glancing or diffraction angle.
 Figure 3: Schematics of X-ray diffractometer

Klug and Alexander have given detailed treatments of X-ray diffraction analysis. The Debye
Scherer method in conjunction with diffractometer is most usually used. The diffracted radiation
is detected by the counter tube, which travels along the angular range of reflections. An inbuilt
program on a computer system processes the observed intensities. A diffraction pattern
consisting of d values of existing atomic planes in the sample and corresponding reflected
intensities is made accessible.
Identification of phases can be done in a following way: The observed d-values are
compared with standard d-values from JCPDS diffraction pattern, for the same material
synthesized by standard chemical techniques. This analysis shows the different phases present in
the sample and Miller indices of the atomic planes. The lattice parameters a, b and c for the unit
cell of the phase present are then calculated using equations given by W.M. Chine. The
proportional amount of phases present can be determined from entire intensities. The structure
of the film sample, if it is a binary system, can be determined from the lattice parameters using
Vegard’s law. Absence of reflection peaks indicates the amorphous nature of the sample. A
single reflection peak specifies an epitaxial growth, while many reflection peaks show
heteroepitaxial (polycrystalline) growth. Fig.2 shows photograph of the Bruker D2-Phaser X-ray
diffractometer.
In case of a polycrystalline sample having large number of grains, the grain size is
determined from Scherer’s formula,
d= 0.9 λ / β Cosθ
Where,  = Wavelength of X- rays
  = Bragg’s angle
 = Full width at half maximum (FWHM) (in radian) of the peak intensity.

Figure 4: Photograph of the Bruker D2-Phaser X-ray diffractometer

3.3 UV-VIS Spectroscopy

Principle of ultraviolet-visible absorption
Molecules containing π-electrons or non-bonding electrons (n-electrons) can absorb the
energy in the form of ultraviolet visible light to excite these electrons To higher anti-bonding
molecular orbital .The more easily excited the electrons, the longer the wavelength of light it can
absorb.

Beer–Lambert law
The Beer-Lambert law (also called the Beer-Lambert-Bouguer law or simply Beer's law) is the
linear relationship between absorbance and concentration of an absorber of electromagnetic
radiation. The general Beer-Lambert law is usually written as:
A=aλ·b·c
where A is the measured absorbance, aλ is a wavelength-dependent absorptivity coefficient, b is
the path length, and c is the analyte concentration. When working in concentration units of
molarity, the Beer-Lambert law is written as:
A = el · b · c
where el is the wavelength-dependent molar absorptivity coefficient with units of M -1 cm-1. The
λ subscript is often dropped with the understanding that a value for ε is for a specific
wavelength. If multiple species that absorb light at a given wavelength are present in a sample,
the total absorbance at that wavelength is the sum due to all absorbers:
A = (ε1 · b · c1) + (e2 · b · c2) +...
Where, the subscripts refer to the molar absorptivity and concentration of the different absorbing
species that are present.

Figure 5: Photograph of Shimadzu UV-1800 UV-Vis Spectrophotometer

Fig. 5 shows the photograph of Shimadzu UV-1800 UV-Vis spectrophotometer. The

equilibrium charge carrier distribution of any material (conductor, semiconductor or insulator)
can be disturbed by its exposure to electromagnetic radiation of appropriate energy. The
photons occurrence of any material may be reflected (R), transmitted (T) or absorbed (A).
The quantity of radiation of wavelength  absorbed by a material slab of thickness t is
measured in terms of optical density (t). Assuming negligible reflection (R=0), the energy
absorbed can be given by Lambert’s equation,
I  I0exp(αt)
Where, I and Io are incident and transmitted intensities respectively.
The optical absorption coefficient of films is evaluated from transmittance as
T  Aexp(αt)
Where T is the transmittance, t is the film thickness, A is a coefficient related to the refractive
index, which is nearly equal to unity at the absorption edges and  is the absorption coefficient.
The equilibrium situation in a semiconductor can be disturbed by a generation of carriers
due to optical photon absorption. The phenomena of radiation absorbed in a material are
altogether considered to be due to 1) inner shell electrons 2) valence band electrons 3) free
carriers including holes as well as electrons and 4) electrons bound to localized impurity centres
or defects of some type. To study the fundamental properties of semiconductor materials, the
absorption of the second type of electrons is of enormous importance. In an ideal
semiconductor, at absolute zero temperature, the V.B would be completely full of electrons, so
that electron could not be excited to a higher energy state from the V.B. Absorption of quanta of
sufficient energy tends to transfer the electrons from V.B to C.B. The optical absorption spectra
of semiconductors generally exhibits a sharp rise at a certain value of the incident photon energy
which can be attributed to the excitation of electrons from the valence to the conduction band
(may also involve acceptor or donor impurity levels, traps etc.). The preservation of energy and
momentum must be satisfied in optical absorption procedure. Fundamentally, there are two
types of optical transitions that can occur at the fundamental edge of the crystalline
semiconductor, direct and indirect transitions. Together contain the interaction of an
electromagnetic wave with an electron in the V.B, which is across the fundamental gap in the
C.B. However, indirect transition also involves simultaneous interaction with lattice vibration.
Wave vector of the electron can change in the optical transition. The momentum change being
taken or assumed up by phonon. Direct interband optical transition contains a vertical transition
of electrons from the V.B to the C.B such that there is no change in the momentum of the
electrons and energy is conserved which is shown in Fig.

Figure 6: E-k diagrams showing (a) direct and (b) indirect inter-band transition.

The photon absorption of a material is characterized by means of electron transition

between energy states or bands according to quantum rules. An ideal semiconductor, at
moderate temperature has small number of holes in the valence band electrons in the conduction
band. Absorption of photons of appropriate energy tends to transfer the electrons from the
valence band to the conduction band giving absorption maxima. Therefore, the optical
absorption spectrum of a pure semiconductor exhibits a fundamental absorption edge at a certain
incident photon energy, which can be ascribed to the excitation of electrons from the valence to
the conduction band separated by energy equal to the band gap energy (Eg). The photon energy
dependence at the absorption edge is given by .
(h)  B(h E ) n g

where hν is the incident photon energy, B is the absorption edge width and n is exponent that
governs the type of electronic transition producing absorption, which is 1/2, 3/2, 2, 3 for direct
forbidden, direct allowed, indirect allowed and indirect forbidden transitions, correspondingly.
The band gap energy of the films can be gained by extrapolating the linear region of the plots
(h)n to zero absorption coefficient i.e. it extrapolates at α=0.

3.4 Scanning Electron Microscopy (SEM)

The scanning electron microscope (SEM) uses a focused beam of high-energy electrons
to generate a variety of signals at the surface of solid specimens. The signals that derive from
electron-sample interactions reveal information about the sample including external
morphology (texture), chemical composition, and crystalline structure and orientation of
materials making up the sample. In most applications, data are collected over a selected area of
the surface of the sample, and a 2-dimensional image is generated that displays spatial
variations in these properties. Areas ranging from approximately 1 cm to 5 microns in width
can be imaged in a scanning mode using conventional SEM techniques (magnification ranging
from 20X to approximately 30,000X, spatial resolution of 50 to 100 nm). The SEM is also
capable of performing analyses of selected point locations on the sample; this approach is
especially useful in qualitatively or semi-quantitatively determining chemical compositions
(using EDS), crystalline structure, and crystal orientations (using EBSD). The design and
function of the SEM is very similar to the EPMA and considerable overlap in capabilities exists
between the two instruments.

Fundamental Principles of Scanning Electron Microscopy (SEM)

Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this energy is
dissipated as a variety of signals produced by electron-sample interactions when the incident
electrons are decelerated in the solid sample. These signals include secondary electrons (that
produce SEM images), backscattered electrons (BSE), diffracted backscattered electrons
(EBSD that are used to determine crystal structures and orientations of minerals), photons
(characteristic X-rays that are used for elemental analysis and continuum X-rays), visible light
(cathode luminescence–CL), and heat. Secondary electrons and backscattered electrons are
commonly used for imaging samples: secondary electrons are most valuable for showing
morphology and topography on samples and backscattered electrons are most valuable for
illustrating contrasts in composition in multiphase samples (i.e. for rapid phase discrimination).
X-ray generation is produced by inelastic collisions of the incident electrons with electrons in
discrete orbital (shells) of atoms in the sample. As the excited electrons return to lower energy
states, they yield X-rays that are of a fixed wavelength (that is related to the difference in
energy levels of electrons in different shells for a given element). Thus, characteristic X-rays
are produced for each element in a mineral that is "excited" by the electron beam. SEM
analysis is considered to be "non-destructive"; that is, x-rays generated by electron interactions
do not lead to volume loss of the sample, so it is possible to analyze the same materials
repeatedly.

Figure 7: Schematic of a scanning electron microscope (SEM)

Working
The scanning electron microscope (SEM) is a microscope that works by scanning a focused
beam of electrons on a sample of interest. The main SEM components include:

 Source of electrons
 Column down which electrons travel with electromagnetic lenses
 Electron detector
 Sample chamber
 Computer and display to view the images
Electrons are produced at the top of the column, accelerated down and passed through a
combination of lenses and apertures to produce a focused beam of electrons which hits the
surface of the sample. The sample is mounted on a stage in the chamber area and, unless the
microscope is designed to operate at low vacuums, both the column and the chamber are
evacuated by a combination of pumps. The level of the vacuum will depend on the design of the
microscope.

The position of the electron beam on the sample is controlled by scan coils situated above the
objective lens. These coils allow the beam to be scanned over the surface of the sample. This
beam restoring or scanning, as the name of the microscope suggests, enables information about
a defined area on the sample to be collected. As a result of the electron-sample interaction, a
number of signals are produced. These signals are then detected by appropriate detectors.
 Image 2: Electronic Balance

4.3 pH Indicator

Image 3: pH Indicator

In my project synthesis of the sample is carried out at neutral condition. Hence to adjust pH
equal to7. Liquid ammonia is added slowly in the solution by using a dropper and pH is checked
by using indicator paper.

4.4 Magnetic Stirrer and Heater

Image 4: Magnetic Stirrers and Heater

It is used for heating and stirring solution which works on the magnetic principle. In which
temperature can be set as we desired and stirring rate rpm can be adjusted. This is available in
many models. We have used simple one which stirring rate in rpm can be adjusted and it is
displayed on display.

4.5 Preparation of Solution

Calculations:

The atomic weight of constituents

General formula: Total weight = [mol. Weight* Molarity*wt. of solution (ml)]/1000

0.5 molarity = [molecular weight * 100ml *0.5] /1000

Given:-
1) Wt. of Zinc acetate [(CH3.COO) 2 Zn.2H2O] = (219.50*0.5*100)/1000 =10.975gm

2) Wt. of Thiourea [SC (NH2)2] = (76.12*0.5*100)/1000 =3.806gm

Zinc acetate and thiourea adding the ammonia for this process

Procedure:-

 Prepare the zinc acetate of 0.5 molarity.

 Add this zinc acetate into 100 ml of distilled water.
 Add ammonia into this solution drop wise upto its Ph gets in between 9.5 to 10.5.
 Then add 0.5 molarity of thiourea in this solution.
 Then kept this solution on the magnetic stirrer for 1 hour at 570c temperature.
4.6 EXEPERIMENTAL PROCEDURE

Figure 9: Flow chart of Preparative Method

CHAPTER 5: RESULT AND DISCUSSION

5.1 XRD Result of ZnS Thin Film

1200

(112)

(200)
1000

(220)

(312)
800
Intensity (A. U.)

600

400

200

0
20 40 60 80
2  (Degree)

Figure 10: XRD of ZnS thin film

The XRD pattern of the as-deposited and annealed ZnS film on glass substrate at different temp.
i.e. 1000C and 800C was shown in Fig. 10. The curve shows the XRD pattern of bare glass
substrate. The diffraction pattern of the as-deposited ZnS film exhibited peaks corresponding to
the (1 1 2), (2 0 0), (2 2 0) and (3 1 2) plane of the cubic ZnS phase.

5.2 Particle size from Full Width half maxima (FWHM)

In this present work Synthesis of Zinc Sulphide by CBD method carried out. From XRD result
we get a particle size (For prominent peak 112) is 35.2 nm.
5.3 SEM Results of ZnS

Figure 11: SEM Images of ZnS thin film

Fig. 11 shows the SEM of ZnS films grown on various growth phases. ZnS film formed in the
none-film phase shows the grains are discontinuous. ZnS film formed in quasi-linear phase
shows a compact and a granular structure with the grain size about 100 nm.

5.4 UV Result

1.00E+011

8.00E+010 Band gap of ZnS= 3.7 eV

6.00E+010
hv)2(eV/cm)2

4.00E+010

2.00E+010

0.00E+000
2.0 2.5 3.0 3.5 4.0

hv(eV)

Figure 12: Band gap energy of ZnS thin film

 For the indirect transition, the optical band gap energy of ZnS thin film is determined
by using the Tauc equation,

h  E  2

  Const. g

h
1/2
Where, hν is the photon energy and Eg the band gap energy. Fig.12 shows plots of (αhν) Vs
hν of ZnS thin films. Band gap energy of ZnS is 3.7 eV. Which is useful for further
application.
CHAPTER 6: CONCLUSION

In this work, we have presented the preparation of high quality films of closely packed
nanocrystals of ZnS by CBD ammonia-free method using thiourea as sulfide ions source and
zinc acetate as a complexing agent for zinc ions in an almost neutral bath solution. The XRD
patterns exhibited the cubic zinc blend structure for ZnS and no other crystalline phases were
detected. The film thickness can be controlled by the duration of deposition and/or multiple
depositions. The direct band gap of as-deposited films ranged from 3.78 eV. When annealing
temperature increases, the crystal size increases and consequently the band gap energy
decreases.
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